Accepted Manuscript

Can Portland cement be replaced by low-carbon alternative materials? A study on

thermal properties and carbon emissions of innovative cements

Riccardo Maddalena, Jennifer J. Roberts, Andrea Hamilton

PII: S0959-6526(18)30450-5
DOI: 10.1016/j.jclepro.2018.02.138
Reference: JCLP 12085

To appear in: Journal of Cleaner Production

Received Date: 4 August 2017

Revised Date: 5 December 2017
Accepted Date: 13 February 2018

Please cite this article as: Maddalena R, Roberts JJ, Hamilton A, Can Portland cement be replaced by
low-carbon alternative materials? A study on thermal properties and carbon emissions of innovative
cements, Journal of Cleaner Production (2018), doi: 10.1016/j.jclepro.2018.02.138.

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wordcount: 5020 words, 9 Figures, 3 Tables

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Can Portland cement be replaced by low-carbon alternative
materials? A study on thermal properties and carbon emissions

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of innovative cements

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Riccardo Maddalenaa , Jennifer J. Robertsa , Andrea Hamilton*a
a
University of Strathclyde, Department of Civil and Environmental Engineering, Glasgow G1 1XJ,
UK

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*corresponding author: andrea.hamilton@strath.ac.uk

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Abstract
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One approach to decarbonising the cement and construction industry is to replace or-
dinary Portland cement (OPC) with lower carbon alternatives that have suitable prop-
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erties. We show that seven innovative cementitious binders comprised of metakaolin,

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silica fume and nano-silica have improved thermal performance compared with OPC
5 and we calculate the full CO2 emissions associated with manufacture and transport of
each binder for the first time. Due to their high porosity, the thermal conductivity
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of the novel cements is 58–90% lower than OPC, and we show that a thin layer (20
mm), up to 80% lower than standard insulating materials, is enough to bring energy
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emissions in domestic construction into line with 2013 Building Regulations. Carbon
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10 emissions in domestic construction can be reduced by 20–50% and these cementitious

binders are able to be recycled, unlike traditional insulation materials.
Keywords: cement industry, nano-silica, carbon footprint, thermal conductivity.

Preprint submitted to Journal of Cleaner Production February 15, 2018

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1. Introduction

Ordinary Portland cement (OPC) is one of the most manufactured materials in

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the world. Over 3 billion tonnes of cement were manufactured in 2012 [1], and global
15 demand is expected to increase due to rapid infrastructural development of emerg-

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ing economies [2, 3]. Indeed, global cement production is forecast to reach 3.7–4.4
billion tons by 2050, as stated by the World Business Council for Sustainable Devel-

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opment (WBCSD) report in 2009 [4]. Cement is primarily used by the construction
and geotechnical industries, but there are other emerging applications, including nu-
clear waste containment, biological and dental ceramics, and water filtration. Cement

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clinker is produced by calcining limestone (or marl or chalk) with some clay in a fur-
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nace at c. 1500 ◦ C and is a significant source of greenhouse gas emissions (GHG),
which are usually expressed as CO2 equivalent (CO2eq ) and sometimes referred to as
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”embedded carbon” [5]. Approximately 900 kg of CO2eq is released per ton of cement
25 produced by current practices [6]. Thus, the cement industry is estimated to contribute
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5–7% of global anthropogenic CO2 emissions in 2009 [7]. The direct release of CO2
from calcination during clinker production is responsible for c. 50% of the emissions
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from cement manufacture (Figure 1). Much of the remaining emissions come from
the combustion of fossil fuels for calcination, plus excavation, transportation, milling
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30 and grinding processes. Given the global effort to curb CO2 emissions in an attempt
to mitigate dangerous climate change effects [8] (for example the 2015 Paris Agree-
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ment, a framework for an internationally coordinated effort to tackle climate change),

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and the expected rise in global demand for cement, reducing emissions from cement
manufacture presents an important challenge. Indeed, the ’decarbonisation’ of cement
35 production is becoming a more prominent issue for the cement sector, as evidenced by
the WBCSD and International Energy Agency (IEA) Cement Roadmap (2009), the
Industrial Decarbonisation & Energy Efficiency Roadmaps to 2050 report and British

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Cement Association (BCA73 Carbon Strategy 2005) [4, 9, 10].

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Figure 1: Simplified diagram of the cement production process. Red circles indicate the percentage
of CO2eq emissions associated with manufacturing. (∗)
50% of the emissions associated with pyropro-
cessing arises from direct release of CO2 from calcination and the remaining 35% from fuel and energy
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consumption. [Image adapted from Imbabi et al., (2012)[1]]
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Researchers and industry have focused their attention on using alternative fuels in
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40 place of conventional fossil fuels (and so reducing the GHG emissions of the traditional
OPC manufacturing process), and developing alternative materials by partially replac-
ing Portland cement with fly ash[11]. Alternative materials that have been developed
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or tested include reused waste (such as industrial by-products like fly ash or biomass
wastes like rice husk ash), alkali materials (such as red mud) and novel binders such as
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45 geopolymers or alkali-activated cement [12, 13, 7, 14, 15, 16]. Since these novel binders
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have low or negative carbon emissions associated with their production, they are some-
times referred to as ”green cements” [17]. In most cases, the alternative materials only
partially replace clinker. This is advantageous from a regulatory perspective since the
existing standardised codes of practice for OPC can be adapted or built upon. It is
50 important that the mechanical properties of alternative cements are similar to (or more

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advantageous than) the properties of OPC. Recent studies have found that some OPC
novel binder mixtures such as lime-metakaolin have suitable properties [18] and might
be preferable to OPC in humid environments [19]. Other novel additives such as sil-

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ica fume and nano-silica particles improve the properties of OPC [20, 21, 22, 23] and
55 metakaolin-based geopolymers [24, 25]. The main reason geopolymer binders have not

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yet been more widely adopted by industry is the current lack of regulatory standards
backed by long term testing and development [26].

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OPC is used in the preparation of mortar for wall rendering/finishing and also in
aerated concrete blocks employed as a thermal insulation material [27, 28]. However,

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60 aerated OPC does not offer thermal conductivity values comparable to other solutions
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on the market, such as polymer foam, glass fibres and vacuum insulation panels [29].
Although these materials have very low thermal conductivity, in the range 0.01–0.002
W/(m K) [30, 31], which can help reduce energy consumption, their production is
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polluting [32, 33] plus they cannot entirely be recycled and have to be disposed of in
landfill. Geopolymer binders and OPC-free mixtures have been proposed as alternative
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insulation materials to OPC-based composites and have shown thermal conductivity

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values, 0.17–0.35 W/(m K), lower than traditional cement mortar or concrete (0.2–0.8
W/(m K) [34]) although not comparable with insulation materials such as glass fibres
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or polymers [25].
70 Life cycle analyses on selected geopolymer binders have found that their use in place
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of OPC could reduce GHG emissions from the cement industry by 9–64% [35, 7]. How-
ever, these life cycle emissions are context and country dependent and often subjected
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to availability of raw materials [36, 37, 38]. To date, the environmental sustainability
of a range of OPC free cement mixtures has not been comparatively explored, nor has
75 there been a comprehensive analysis of properties of alternative cements and their po-
tential to completely replace OPC. Here we consider the carbon reduction that could be

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achieved by using seven alternative cementitious materials in place of OPC, evaluate

CO2eq gas emissions of OPC and geopolymer production, taking the whole life-cycle
into account, including the transport of raw materials and the manufacturing process

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80 [1].
The aim of this work is to develop novel ’green’ cementitious materials with superior

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thermal properties to ordinary Portland cement and low environmental impact. Silica
particles, metakaolin and calcium hydroxide are combined in binary or ternary sys-

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tems and their physical, thermal and mechanical properties are characterised. Thermal
85 performance is calculated in the context of a typical domestic construction and a com-

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parison of GHG emissions for these novel cementitious binders and OPC is presented
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for the first time in the UK-European context. These OPC-free cements represent
an environmental friendly alternative with a high recyclability potential, simple man-
ufacturing process and able to ensure thermal comfort within current international
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90 standards. Furthermore, GHG emissions are calculated following a simplified life cycle
assessment, which provide a useful decision-making tool to industries or practitioners
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to rapidly calculate the carbon footprint of novel OPC-free binders.

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2. Materials and methods

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2.1. Materials

95 Portland cement samples were prepared using ordinary Portland cement CEM I
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42.5-R (CAS number 65997-15-1), commercially available from the Lafarge Cement
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Group, and deionised water (W). Physico-chemical properties of Portland cement are
listed in Table S1 of the Supplementary Material. Cement samples (OPC) were pre-
pared with a liquid to solid (l/s) ratio of 0.3 using a rotary mixer according to BS
100 EN 196-1:2016 and cast into cubic moulds for 24 hours. After 24 hours samples were
kept for 28 days at relative humidity of 98 ± 2% and temperature of 21 ± 2 ◦ C in a

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nitrogen gas environment to minimise carbonation prior to testing. Novel OPC-free

cement samples were prepared using different starting materials. Reagent grade cal-
cium hydroxide, Ca(OH)2 (CAS Number 1305-62-0) and Ludox T50 nano-SiO2 aqueous

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105 suspension (CAS number 7631-86-9) were purchased from Sigma Aldrich. Silica fume
(CAS number 69012-64-2), commercially available as SF920D from Elkem Microsilica

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(Norway), was used. Metakaolin was obtained from calcination of kaolin (China clay
type purchased from Imerys UK, CAS number 1332-58-7) at 750 ◦ C over 24 hours, as

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described by Alonso et al. [39]. Reagent grade sodium hydroxide, NaOH (CAS num-
110 ber 1310-73-2) of nominal concentration 10 M was purchased from Fisher Chemical.

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Chemical and physical properties of the starting materials (calcium hydroxide (CH),
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nano-silica (NS), metakaolin (MK), silica fume (SF)) are reported in Table S2 of the
Supplementary Material. Given the pozzolanic reactivity of nano-silica and amorphous
silica fume, binary mixes using calcium hydroxide and silica (nano-silica or silica fume)
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115 were investigated (samples CHI, CHI10, CHNS). Alkali activated binders were prepared
mixing metakaolin with calcium hydroxide in different proportions. Sodium hydroxide
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10 M was added as an activator (sample MK10, AMK, BMK). Finally metakaolin was
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mixed with nano-silica and calcium hydroxide, using lower concentration NaOH (1 M)
as activator (sample MKNS). Mix proportions and sample identification are listed in
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120 Table 1. Fresh paste was cast into cubic moulds and specimens were kept for 28 days
at relative humidity of 98 ± 2% and temperature of 21 ± 2 ◦ C in a nitrogen gas en-
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vironment to minimise carbonation. Sample MK10 was thermally prepared following

the methodology of Zhang et al. (2014) for geopolymers [40]. After mixing, specimens
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were cast into a cubic mold and kept in an oven at 60 ◦ C and atmospheric pressure for
125 24 hours, then placed in a sealed environment for 28 days at relative humidity of 98 ±
2% and temperature of 21 ± 2 ◦ C.

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Table 1: Sample name, mixes and proportion

Sample OPC CH NS SF MK W NaOH 10 M NaOH 1 M

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% l/s ratio
OPC 100 - - - - 0.3 - -

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CHI - 75 - 25 - 0.6 - -
CHI10 - 75 - 25 - - 0.8 -

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MK10 - - - - 100 - 0.8 -
AMK - 75 - - 25 - 1 -

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BMK - 66 - - 33 - 1 -
MKNS - 10 5 - 85 - - 1
CHNS - 50 50 -
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2.2. Physical, thermal and mechanical properties

After ageing for 28 days samples were removed from the mold and dried at 60 ◦ C to
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remove pore water and perform mechanical tests and micro-structural analyses. Water
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130 removal has an impact on the microstructure, therefore analysis and results presented
should be regarded comparatively. Compressive strength testing was performed accord-
ing to BS EN 196-1:2016, using a uniaxial compressive testing machine at a constant
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strain rate of 0.4 mm/min until fracture [21, 41]. Three specimens of each compos-
ite were tested. The resistance value (Rc ) is given in MPa as a mean value of three
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135 replicates for each mixing. The heat of hydration was measured using an isothermal
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calorimeter (I-Cal 4000 HPC, Calmetrix). Fresh paste (c. 60 g) was cast into a cylindri-
cal container and placed into the calibrated calorimeter, at a constant temperature of 21
± 2 ◦ C. The heat flow was recorded over 80 hours. Open porosity (ϕ) was estimated by
measuring the total water content in each sample (in three replicates) after oven-drying
140 at 60 ◦ C and overnight saturation in a vacuum chamber. Open porosity was calculated

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using the equations reported in the Methods section of the Supplementary Material.
For each sample the laser flash method (LFA) was used to estimate the coefficient
of thermal conductivity (λ), given in W/(m·K). A Netzsch instrument 427 LFA was

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used. Samples of each composition were tested in an argon atmosphere and thermal
145 conductivity was calculated at 25◦ , 60◦ and 105 ◦ C according to the BS EN 821-2:1997.

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The coefficient of thermal conductivity was estimated using the laser flash method.
The specimens were powdered and pelletized using an hydraulic press to make pellets

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of 12.7 mm and 3 mm thickness. The surface was coated with graphite to min-
imise reflectance of the laser beam. A pyroceramic standard supplied by Netzsch was

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150 analysed and used as a reference material to calculate the specific heat capacity and
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thermal diffusivity. Thermal conductivity was calculated at 25◦ , 60◦ and 105 ◦ C, as a
function of the open porosity, using the equations reported in the Methods section of
the Supplementary Material.
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In order to evaluate the insulation properties of these novel cement composites, the
thermal transmittance (U ) of a typical wall was calculated, using the equations reported
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in the Methods section of the Supplementary Material. An external wall (1 m high and
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1 m wide) of standard domestic construction was considered, as shown in Figure 6

(left). The wall consists (from outdoor to indoor) of horizontal bricks (225×112×65
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mm BS EN 771-1:2011, λ=0.84 W/(m K)) with a 5 mm layer of cement mortar (λ=1.4

160 W/(m K), [30]) and externally finished with 18 mm thickness of mortar render (λ=1.4
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W/(m K)). Adjacent to the outer brick skin is a 20 mm thick air cavity (λ=0.03 W/(m
K)), 9 mm layer of plywood (λ=0.14 W/(m K)), a rock-wool insulation wall of 40
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mm thick (λ=0.04 W/m·K, [29]) and a 15 mm thick gypsum plaster board (λ=0.21
W/(mK), [30])finished with 2 mm thick waterproof plaster painting (λ=0.09 W/(m
165 K), [30]). The wall is then finished with an outside mortar render and internal plaster.
This is a pattern in the construction that repeats itself every 70 cm in the vertical

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direction. Therefore a 1 m wide and 0.7 m high portion of the wall was considered,
as it is representative of the entire wall. One-directional heat transfer and constant
thermal conductivity values are assumed.

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170 2.3. Powder X-Ray Diffraction and Scanning Electron Microscopy

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Powder XRD analyses were performed using a Bruker D8 Advance diffractometer
with CuKα radiation over the range 5–60◦ 2θ, step size of 0.02◦ 2θ and 0.5 s/step.

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DiffracEva software from Bruker was used for XRD pattern evaluation and phase iden-
tification. Microstructural analysis of samples was carried out using Scanning Electron

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175 Microscopy (W-SEM, Hitachi S-3700N and FE-SEM, Hitachi SU6600) with Energy
Dispersive Spectroscopy (EDS, Oxford INCA-7260) at an accelerating voltage of 10–15
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kV. All samples were resin impregnated, polished and gold coated.
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2.4. Greenhouse gas emission assessment

Calculation of the total greenhouse gas emission (GHG), expressed as carbon diox-
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180 ide equivalent (CO2eq ) per 1000 kg of cement produced, takes into account the collective
contribution of CH4 , NOx , SOx , CO2 and synthetic gases evolved during production
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activity, including excavation and transport of raw materials and reagents, and man-
ufacturing. The approach to estimate the total GHG is based on the methodology
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reported in McLellan et al. (2011) [35] and calculated using the equation 1:
n
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GHGT ot = mi (di ei + pi ) (1)
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i=1
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185 where GHGT ot is the total greenhouse gas emission (kgCO2eq ) per ton of material pro-
duced, mi is the fraction of component i, di is the distance transported by a given mode
of transport (km), ei is the emission factor for the transportation mode (kgCO2 eq /(km
ton)) and pi is the emissions per unit mass of component i produced (kgCO2 eq /ton).
The following assumptions were made in the analysis:

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190 1. The calculations were based on the manufacture of 1 ton of Portland cement
binder and 1 ton of novel materials in the United Kingdom, using, where possible,
UK products, otherwise materials from a typical supply chain.

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2. Previously published values for CO2eq emissions from the manufacture of the raw
materials were used, and added to the emissions from transport to and within the

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195 UK.
3. The emissions due to the addition of water to cement paste are very low (0.271

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kgCO2 eq /ton [42]) therefore negligible and not taken into account.
4. Maximum distances and mode of transport are selected as those which maximise

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CO2eq emissions, because this work adopts the worst-case scenario for CO2eq emis-
200 sions. AN
5. Emission factors associated with road transport (er ) and sea transport (es ) are
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respectively 0.09 kgCO2 eq /(km ton) and 0.02 kgCO2eq /(km ton) [35, 43].
6. Emissions per unit mass of OPC (pOP C ) are 750 kgCO2eq /ton and is produced in
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mainland UK.
7. Emissions per unit mass of metakaolin (pM K ), produced in England and silica
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fume (pSF ), produced in Norway, are respectively 236 kgCO2eq /ton and 7×10−6
kgCO2eq /ton [44, 35].
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8. The manufacture of calcium hydroxide is based on the hydration of calcium ox-

ide, produced in Northern Ireland, (pCO =750 kgCO2eq /ton) taking into account a
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210 correction factor of 0.97 due to the addition of water (pCH =720 kgCO2eq /ton) as
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explained in the IPCC Guidelines for national greenhouse gas emissions [45].
9. Sodium hydroxide is produced in Northern Ireland by a chemical process using
electrolytic cells. The emissions associated with the production are in the range
1120–1915 kgCO2eq /ton as reported for a nominal concentration of 16 M [7, 43, 46].
215 In order to take into account lower sodium hydroxide concentrations, we used a

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correction factor of 0.43 and 0.63 respectively for NaOH 1 M and NaOH 10 M
on the lowest emission value (pN aOH =1120 kgCO2eq /ton), following the principle
of the IPCC guidelines [45].

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10. Nano-silica solution is manufactured in Germany and the carbon emissions value
can be obtained from the manufacture of sodium silicate solution (pN S =386

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kgCO2eq /ton) [47, 48, 23].

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A schematic diagram of mode of transport and distances for each raw material is shown
in Figure 2.

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3. Results and discussion

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3.1. Physical, thermal and mechanical properties
The particle size and the high specific surface area of nano-particles play an impor-
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tant role in the physical and mechanical properties. The measured bulk density (%),
matrix density (%mat ), open porosity (ϕ), compressive strength (Rc ) results and cumu-
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lative heat released values are reported in Table 2. All the mixes show values of bulk
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230 density in the range 600–1100 kg/m3 , much lower than standard OPC (1900 kg/m3 ).
Density and porosity values are in good agreement with literature data on lightweight
materials such as calcium silicate boards and aerated concretes [49, 50, 51]. Sample
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CHI10 shows a higher bulk density and lower porosity due to the greater l/s ratio and
the presence of an alkaline activator. Samples MK10, AMK and BMK show decreasing
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235 density values directly proportional to the content of metakaolin, from 100% to 66%. On
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the other hand porosity increases when a lower amount of MK is used (sample MKNS)
and higher concentration of nano-silica is used (sample CHNS). Mechanical tests per-
formed on all the samples after 28 days of curing show values of compressive strength,
in the range of 1.8–7.8 MPa. Although compressive strength values are not comparable
240 with OPC, they satisfy the resistance requirement for non-loaded structures; results

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Figure 2: Diagram of transportation mode and average distance for raw materials in and to UK. Silica
fume (SF) is supplied from Norway, nano-silica (NS) from Germany, calcium hydroxide (CH) and
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sodium hydroxide (NaOH) from Northern Ireland (UK), metakaolin (MK) and Portland clinker are
available in mainland UK.
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are in agreement with the values given for aerated concrete blocks [52, 53] and lime-
metakaolin mortars [54, 55]. Isothermal calorimetry was used to measure the heat flow
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development of the samples at 21 ◦ C. Figure 3 shows the heat flow (in mW/g) of the
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samples compared to OPC. Since the mixing was done externally, the first peak appears
245 at the very beginning of the measurement for all the samples (Figure 3a); it corresponds
to particle wetting and dissolution, the chemical reaction which leads to the formation
of hydrated phases. The second peak appears broad and delayed compared to OPC. It
corresponds to the polymerisation of dissolved species into new crystal structures. In

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sample CHI the first peak converges into a straight horizontal line and no second peak
250 is detected, indicating very low reactivity [56]. Sample CHI10 shows the influence of the
alkali-activator, resulting in higher intensity. Specimen CHNS (CH and NS) shows the

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same trend of mix CHI (CH and SF), with a high first peak converging into a horizontal
line. However a second peak is detected as a broad hump at around 20 hours. This is

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due to the smaller particle size and higher reactivity of NS compared with SF. Sample
MK10 shows a high-intensity broad first peak followed by small broad hump associated

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with the second peak of hydration. Samples AMK and BMK have respectively 75%
and 66% of calcium hydroxide content. In sample BMK, the higher content of MK

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produces a delay in the second peak compared to sample AMK. The peak is higher

260
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in intensity from the increased formation of alkaline aluminosilicate due to the greater
concentration of dissolved aluminum ions [39]. The cumulative heat released in the first
80 hours was obtained by integrating the heat flow curves and is summarised in Table
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2. Except for the mix MK10, with a total heat release of 4.4×105 J/kg, in accordance
with the work of Zhang et al. [57], all the other mixes show a cumulative energy lower
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than OPC, due to the lower number of reactants dissolved. Cumulative heat released
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265 is detailed in Table 2 and shown in Figure S1 in the Supplementary Material. OPC
clinker is a complex mixture of compounds and usually gypsum is added to delay the
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setting time. Therefore the hydration chemistry of OPC involves more ionic species,
resulting in a higher total cumulative heat released.
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Table 2: Bulk density (%), matrix density (%mat ), open porosity (ϕ), compressive strength (Rc ) and
cumulative heat release of all the samples

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Sample ρ ρmat ϕ Rc Heat release
kg/m3 kg/m3 - MPa J/g

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OPC 1940 2460 0.21 51.2 235
CHI 940 2430 0.61 6.4 44

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CHI10 1120 2160 0.48 7.7 211
MK10 1020 2190 0.53 5.2 463
AMK 900 2180 0.59 4.7 75

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BMK 850 2020 0.58 6.5 104
MKNS 640 AN
2260 0.72 1.7 51
CHNS 610 2390 0.74 2.2 238
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Figure 3: Heat flow measurement for each sample. (a) magnification of the first 30 min of heat flow
measurement.

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3.2. Powder X-Ray Diffraction and Scanning Electron Microscopy

270 XRD patterns obtained for the developed materials are presented in Figure S2 in

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the Supplementary Material, where only the major mineral phases are shown. Samples
CHI and CHI10 are mainly crystalline portlandite (P) and semi-crystalline calcium
silicate hydrate gel (C-S-H), the most abundant component of hydrated cement paste

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and responsible for early strength development and hardening [58] or calcium (sodium)
silicate hydrate (C-(N)-S-H)[59, 60]. Semi-quantitative analysis of the XRD patterns

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showed that, despite the high pH, sample CHI10 has 54% C-S-H compared to sample
CHI (61%). The added Na+ concentration takes Ca++ to produce C-N-S-H in addition

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to the C-S-H produced. Some minor carbonated phases are detected, (calcite, carbon,

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and sodium carbonate), arising from surface carbonation. In the mixes containing
metakaolin and calcium hydroxide (sample AMK, BMK and MKNS), stratlingite (St),
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calcium aluminate hydrate (C-A-H) and monocarboaluminate (M) phases are detected,
in agreement with Silva et al. [19]. Stratlingite is the main hydrate phase responsible
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for strength development in lime-metakaolin based materials. An increase of metakaolin

content from 25% to 35% respectively in samples AMK and BMK results in well defined
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285 peaks of stratlingite, and consequently higher compressive strength. Faujasite (F) is the
main crystalline compound in sample MK10 along with C-S-H gel, calcium aluminate
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hydrate and minor stratlingite. In sample MK10, mixing metakaolin with 10 M NaOH
solution promotes alkaline activation and leads to the precipitation of sodium aluminum
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silicate hydrate (N-A-S-H) gel into the mineral structure of faujasite (F) [40, 61]. In
sample MKNS, reducing the concentration of the activator from 10 M to 1 M and the
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addition of calcium hydroxide at ambient temperature results in the precipitation of

semi-crystalline calcium aluminate hydrate (C-A-H), the main phase detected. Sample
CHNS presents broad humps at c. 29◦ and 32◦ 2θ, typical of C-S-H gel [62].
As shown in the SEM images, the developed materials present a highly porous

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295 matrix in agreement with the density and porosity values measured. In sample CHI
the matrix is mainly semi-crystalline C-S-H whereas the presence of NaOH as alkaline
activator in sample CHI10 promotes the formation of C-S-H combined with C-(N)-S-H

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phases, respectively in Figure 4a and Figure 4b. As shown in XRD patterns, alkali-
activation of metakaolin-lime mixes results in formation of calcium aluminate silicate

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300 hydrate (stratlingite) and C-S-H (sample BMK, Figure 4c). Figure 4d shows a semi-
crystalline C-S-H phase forming a complex plate-like structure in sample CHNS.

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(a) FE-SEM image of sample CHI showing (b) W-SEM image of sample CHI10 show-
a poorly crystallised C-S-H phase flake- ing semi-crystalline C-N-S-H phase and

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shaped. [Voltage 15 kV]. natrite needles. [Voltage 15 kV].
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(c) FE-SEM image of sample BMK show- (d) FE-SEM image of sample CHNS show-
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ing a porous microstructure formed by ing a porous microstructure formed by

stratlingite and C-S-H. plate-like C-S-H phase.
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Figure 4: SEM images of (a) sample CHI, (b) sample CHI10, (c) sample BMK, and (d) sample CHNS.
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3.3. Thermal conductivity measurements

Thermal conductivity values at 25◦ , 60◦ and 105 ◦ C calculated according to equation
S5 are shown in Figure 5 and compared to OPC. Values are in the range 0.05–0.26
305 W/(m K), 50–90% lower than OPC. Samples made mixing metakaolin and sodium

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hydroxide (MK10, AMK and BMK) show thermal conductivity values in accordance
with Palmero et al. (2015) and Villaquiran-Caicedo et al. (2015) [51, 25]. Furthermore
samples show an inversely proportional trend to the content of MK 100%, 75% and

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66% wt. respectively. The addition of silica nano-particles has a beneficial effect on
310 the thermal conductivity. Sample MKNS and CHNS in fact show the lowest λ values

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at 25 ◦ C, 0.055 and 0.088 W/(m K) respectively. These values are typical of insulating
materials [63, 30]. This effect is attributed to the nano-silica smaller particle size

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range and greater surface area, which increases the pore volume (ϕ=0.7) and decreases
the pore-size; the overall consequence is an enhanced phonon scattering effect which

U
315 reduces heat transfer [64]. Samples made by mixing CH and SF, either with water
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or alkali-actived show a different thermal behaviour: while sample CHI has a thermal
conductivity value (λ=0.09 W/(m K)) similar to CHNS, sample CHI10 has a higher
λ, suggesting that the alkali-activator (NaOH, 10 M) contributes to the reduction of
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porosity and decreases the thermal transmittance. As shown in XRD patterns, sample
CHI contains C-S-H and portlandite, whereas CHI10 is made of C-S-H, natrite and
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320

portlandite, bound together in a denser and less porous matrix (c. 20% less than CHI).
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U SC
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Figure 5: Thermal conductivity of samples at 25◦ , 60◦ and 105 ◦ C and porosity values.
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Thermal transmittance (U -value) for the typical wall (Figure 6) was calculated to be
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0.32 W/(m K), using equations reported in the Methods section of the Supplementary
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Material. Building Regulation 2013 in England and Wales for refurbishment of existing
325 buildings (domestic and non-domestic use) requires values less than 0.30 W/(m K). The
application of a layer of novel cementitious material can contribute to the reduction of
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the total transmittance below the limit imposed by building regulations, using materials
of relatively simple manufacture. The U -value was then calculated taking into account
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an additional layer of developed material placed in between the bricks and the air cavity.
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330 The thickness was chosen in order to minimise the total transmittance below the limit
of the building regulations. Thickness values of all the mixes are summarised in Table
3. The thickness of insulation material layers used in the construction industry is in
the range of 30–100 mm (e.g. glass fiber, rock-wool or polymeric foam[30]). Here, a 20
mm layer of mix MKNS is required to reduce the total transmittance by 10%, as shown

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335 in Figure 6. Conventional insulation materials such as rock-wool, polystyrene or glass

fibres, are usually placed in layers of approximately 40–80 mm [31, 65].

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U SC
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Figure 6: Typical external composite brick wall of domestic building in United Kingdom. (Left: Wall
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section and temperature (T )profile. Right: Wall-section including a layer of MKNS and temperature
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profile)
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3.4. Life cycle emissions

Previous studies have addressed the need to meet thermal requirements, using high
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thermal resistant polymers or composites, but the carbon footprint associated to their
manufacture is often overlooked [63, 66]). The estimated CO2eq emissions (GHGi ) for
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340

each of the seven cementitious material are reported in Figure 7 and compared to
OPC. These present the ’worst case scenario’, and so the actual CO2eq emissions would
likely be lower than those reported here. The carbon footprint of each component
material is shown in Figure 7a. The calculated values are similar to previously published

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Table 3: Minimum thickness of novel cement to achieve U -value ≤ 0.29 W/(m2 K)

Sample minimum thickness

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mm
CHI 30

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CHI10 80
MK10 50

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AMK 60
BMK 80
MKNS 20

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CHNS 30
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345 estimates for geopolymer binders and concrete in different contexts [35, 7, 43, 46].
The results show that all types of novel cements studied here have lower embedded
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carbon compared to OPC. For example, sample MKNS has the lowest CO2eq emissions
associated with its manufacture, estimated to be half the emissions from OPC. Sample
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AMK, which has the highest embedded carbon among the novel cements, still has 20%
350 lower CO2eq than OPC. The selected raw materials, their world-wide availability coupled
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with minimum manufacturing make these novel binders environmentally competitive

compared to traditional insulators (e.g. 1 ton of extruded polystyrene is responsible for
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1180 kgCO2eq ) [32]. NaOH and CH are the most common ingredients of the alternative
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cements tested here, and the embedded carbon in these materials is similar to clinker
355 (Figure 7a). Thus, it is the relative proportion of low carbon materials such as SF,
MK and NS which determine the overall carbon footprint for each cement. The major
energy expended in the manufacture of NaOH occurs in the electrolysis process followed
by cooling, which has a large electricity requirement. However, recent findings have

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proven that natural highly alkaline materials could be used, with comparatively high
360 mechanical performance [16]. CH is produced by calcination of calcium carbonate
followed by hydration. The CO2 footprint of both materials could be reduced if they

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were produced using alternative source of energy for the electricity required (e.g. wind
turbine, nuclear energy, photovoltaic energy for the manufacture of NaOH) or using

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bio-mass or other green fuel in the pyroprocessing of calcium carbonate.

U SC
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TE
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Figure 7: Total GHG emission and contribution of each raw material for all the mixes. (a) Bubbles
indicate the single component in each mix and the size indicates the GHG emission associated: clinker
(750 kgCO2eq /ton), CH (720 kgCO2eq /ton), SF (0.01 kgCO2eq /ton), NS (390 kgCO2eq /ton), MK (236
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kgCO2eq /ton), NaOH 10 M (700 kgCO2eq /ton), NaOH 1 M (481 kgCO2eq /ton).
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365 3.5. Environmental impact

The low thermal conductivity of the novel cements also present an environmentally
sustainable alternative for purposes such as wall cladding. Improving insulation in
homes and buildings is an important aspect of reducing thermal energy loss and thus in

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turn reducing energy consumption. These innovative binders are also highly recyclable
370 compared to conventional insulating components such as polymeric foams, polystyrene,
polyurethane, rock-wool or vacuum insulation panels. They could be re-used in the

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building industry as construction and demolition waste (CDW), as intended by the Eu-
ropean Waste Framework Directive 2008/98/EC and the EU Framework Programme

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for Research and Innovation Horizon 2020: ’incorporation up to c. 80% of recycled
CDW material to decrease the content of Portland cement used and consequently reduce

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375

the amount of waste to be placed in landfill’. These innovative cements are more en-
vironmentally friendly than OPC and other polymeric plastic insulators, and offer an

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environmental friendly alternative to traditional materials. They require less manufac-

380
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turing and processing and the raw materials and reagents are readily available, which
is important to consider for large-scale production.
Thus, although novel cements cannot replace OPC in all applications, they offer an
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environmentally sustainable alternative for several applications, and there is significant
potential for these materials to contribute towards the decarbonisation of the cement
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industry.
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385 4. Conclusions
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In this study low-carbon cementitious materials have been developed and charac-
terised. Metakaolin, silica fume, nano-silica and calcium hydroxide were combined
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at different ratios to produce ’green’ binders for construction industry. Physical and
mechanical properties were investigated. Compressive strength values (in the range
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390 2–7 MPa) are typical of non-structural cements (mortars, rendering cements, etc.);
density and porosity measurements show that these materials could be used in con-
struction industry as functional building elements. Pozzolanic activity was detected by
isothermal calorimetry and hydrated phases (calcium/aluminum silicate hydrate, fauj-

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asite, stratlingite) were found in XRD diffractograms. SEM images give an insight to
395 the micro-structure, with the presence of semi-crystalline phases (C-S-H) and highly
porous matrix, in agreement with the porosity measurements (0.48–0.74). Samples

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present thermal conductivity (0.05–0.26 W/m·K), in the range of conventional insulat-
ing materials. While previous studies have focused their attention on solely physical

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properties of OPC-free cements and geopolymers, here we brought together innovative
materials able to satisfy thermal performance requirements within environmental stan-

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400

dards. In facts, the addition of a 20 mm layer of sample MKNS to an external wall of

existing housing, contributes to 10% decrease in thermal transmittance, as required by

U
the Building Regulation 2013 in England and Wales. The environmental impact of the

405
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newly developed materials was assessed estimating the greenhouse gas emission associ-
ated to the manufacturing and production; all the sample have a carbon footprint up
to 23–55% lower than OPC. These materials are ’cleaner’ than OPC and help to reduce
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CO2eq emissions. The life cycle analysis presented here is simplistic, and more detailed
life cycle and cost analyses should be the subject of future research to fully understand
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the economic impact of those materials in replacing OPC. However, the methodology
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410 adopted provides the basis for implementing a decision-making tool that can advise on,
or scope in, low-carbon options before a more resource intensive life cycle assessment
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approach is applied. It will be therefore useful to construction companies or private

developers intended to develop non-conventional building materials (e.g. geopolymers,
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alkali-activated cements), not yet regulated by law or international standards.

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415 Supplementary Material

The following data are available free of charge.

• Table S1–S2: Details of physico-chemical properties of starting materials.

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• Figure S1: Cumulative heat release as specific energy.

• Figure S2: X-Ray diffractograms of hydrated mixes.

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420 • Methods for the calculation of open porosity, thermal conductivity and transmit-
tance.

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Acknowledgement

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This work is supported by UK Engineering and Physical Sciences Research Council,
(EPSRC Grant No. EP/L014041/1 - DISTINCTIVE Consortium - Decommissioning,

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425 Immobilisation and Storage soluTIons for NuClear wasTe InVEntories). Data associ-
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ated with research published in this article is accessible at: http://dx.doi.org/10.15129/b74bc130-
e22d-4043-983b-9823139666f2
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• Green cements high in porosity and very low in thermal conductivity are developed.
• They are a low-carbon alternative to traditional insulation materials and mortars.
• A simplified GHG emissions estimation method has been proposed in the UK context.

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